Polymeric tertiary amines



United States Patent 3,281,470 POLYMERIC TERTIARY AMINES Leonard R. Vertnik, Minneapolis, Minn., assignor to General Mills Inc., a corporation of Delaware No Drawing. Filed May 1, 1963, Ser. No. 277,130 7 Claims. (Cl. 260-583) This invention relates to novel polymers and more particularly to novel nitrogen-containing polymers.

The polytertiary amines of the present invention are characterized by the recurring structural unit:

wherein D is a dimeric fat radical and R is selected from the group consisting of aliphatic and aromatic radicals. These polymers are preferably prepared by the alkylation of a polysecondary amine as illustrated by the following equation:

[-N-CH:DGH=] RC1 [-N-CHg-D-CHa-l I I H NaOH R wherein D is as defined above and R is preferably an aliphatic or aromatic hydrocarbon radical having from 1 to carbon atoms.

The polysecondary amines are characterized by the recurring structural unit:

wherein D is as defined above. The polysecondary amines are conveniently prepared by the condensation polymerization of a fatty dinitrile derived from a dimerized fat acid. In addition to the homopolymer products prepared by the homocondensation of a fatty dinitrile, copolymer polysecondary amine products can be prepared by the condensation copolymerization of a fatty dinitrile and a dinitrile coypolymerizable therewith.

The condensation polymerization of the fatty dinitriles is accomplished by hydrogenating a fatty dinitrile under secondary-amine-forming conditions. By secondaryamine-forming conditions is meant that set of hydrogenation conditions under which a fatty nitrile preferentially forms a secondary amine rather than a primary amine. Secondary fatty amines are commercially available products and the conditions necessary to produce them are well understood in the art. Typical reaction conditions utilize hydrogen pressures in the range of to 1000 p.s.i.g. at temperatures in the range of 200 to 290 C.

The preparative reaction is illustrated by the following equation:

where D is a dimeric fat radical and n is the number of recurring units in the polymer chain. As illustrated in the equation, an ammonia by-product is formed. In order to obtain optimum yields of the desired polysecondary amine product the ammonia by-product should be removed. Generally, this is done by sweeping the reaction mixture with hydrogen gas.

Depending on the reaction conditions employed, the polymer products will vary in molecular weight from dimers in which n in the foregoing equation is 2, to high molecular weight products in which n is 40 or greater. The molecular weight of the polymer product can be varied by selection of the reaction conditions. Mild reaction conditions tend to produce lower molecular weight polysecondary amines while extremely severe reactions conditions produce insoluble cross-linked polymers. The lower molecular weight polysecondary amines are readily pourable, viscous liquids which resemble a heavy syrup. They are generally pale amber in color and are readily soluble in most common organic solvents. As the molecular weight increases, the products are generally more viscous, less soluble and darker in color. Products in which n is about 20 are extremely viscous and are difficult to pour even when heated.

A hydrogenation catalyst is employed to prepare the polysecondary amines. Generally, any nitrile hydrogenation catalyst can be employed. The preferred catalysts are Raney nickel and copper-chromite catalysts. Other suitable catalysts include Raney cobalt, platinum, palladium, palladium on charcoal, platinum on charcoal, nickel on kieselguhr, copper-nickel carbonate, cadmiumcopper-zinc chromite, copper-nickel oxide, and the like.

The copper-chromite catalyst" referred to above is often referred to as copper-chromium oxide catalyst. Preparation of copper-chromite catalysts is discussed in an article by Connor, Folkers, .and Adkins, in the Journal of the American Chemical Society, vol. 54, page 138-45 (132) and in Reactions of Hydrogen With Organic Compounds Over Copper-Chromium Oxide and Nickel Catalysts by Homer Adkins, University of Wisconsin Press, Madison, Wisconsin (1937). The nature of this catalyst is further discussed in an article by Adkins, Burgoyne, and Schneider in the Journal of the American Chemical Society, vol. 72, pages 2226-29 (1950). Commercially available copper-chromite catalysts often contain amounts of catalyst stabilizers, e.g., barium oxide, calcium oxide, and magnesium oxide. Catalysts containing such stabilizers can be employed if desired. While many types of copper-chromite catalysts are commercially available and are generally useful in preparing polysecondary amines, it is preferred to employ a catalyst containing 40 to 65% CuO (assuming all copper is present as CuO) and 35 to 60% Cr O (assuming all chromium to be present as Cr O The amount of catalyst employed is not critical. However, the molecular weight and other properties of the polymer product will vary depending on the amount and type of catalyst used. Generally, catalysts in the amount of l to 10% by weight, based on the weight of the nitrile charge, are sufficient for most purposes. Larger and smaller amounts of catalysts can be employed if desired.

The dinitrile starting materials for preparing the polymeric sec-ondary amines are the dinitriles prepared from dimerized fat acids. Relatively pure dimerized fat acids can be distilled from commercially available polymeric fat acids mixtures. The term polymeric fat radical as used herein refers to the hydrocarbon radical of a polymeric fat acid. The term polymeric fat acids refers to a polymerized fat acid. The term fat acid as used herein refers to naturally occurring and synthetic monobasic aliphatic acids having hydrocarbon chains of 824 carbon atoms. The term fat acids, therefore, includes saturated, ethylenically unsaturated and acetylenically unsaturated acids. Polymeric fat radical is generic to the divalent, trivalent and polyvalent hydrocarbon radicals of dimerized fat acids, trimerized fat acids and higher polymers of fat acids, respectively. These divalent and trivalent radicals are referred to herein as dimeric fat radical and trimeric fat radical.

The saturated, ethylenically unsaturated, and .acetylenically unsaturated fat acids are generally polymerized by somewhat different techniques, but because of the functional similarity of the polymerization products, they all are generally referred to as polymeric fat acids.

Saturated fat acids are difficult to polymerize but polymerization can be obtained at elevated temperatures with a peroxidic catalyst such as di-t-butyl peroxide. Because of the low yields of polymeric products, these materials are not commercially significant. Suitable saturated fat acids include branched and straight acids such as caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, isopalmitic acd, stearic acid, arachidic acid, behenic acid, and lignoceric acid.

The ethylenically unsaturated acids are much more readily polymerized. Catalytic or non-catalytic polymerization techniques can be employed. The non-catalytic polymerization generally requires a higher temperature. Suitable catalysts for the polymerization include acid or alkaline clays, di-t-butyl peroxide, boron trifluoride and other Lewis acids, anthraquinone, sulfur dioxide andthe like. Suitable monomers include the branched and straight chain, polyand mono-ethylenically unsaturated acids such as 3-octenoic acid, ll-dodecanoic acid, linderic acid, lauroleic acid, myristoleic acid, tsuzuric acid, palmitoleic acid, petroselinic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, cetoleic acid, nervonic acid, linoleic acid, linolenic acid, eleostearic acid, hiragonic acid, moroctic acid, timnodonic acid, eicosatetraenoic acid, nisinic acid, scoliodonic acid, and, chaulmoogric acid.

The acetylenically unsaturated fat acids can be polymerized by simply heating the acids. Polymerization of these highly reactive materials will occur in the absence of a catalyst. The acetylenically unsaturated acids occur only rarely in nature and are expensive to synthesize. Therefore, they are not currently of commercial significance. Any acetylenically unsaturated fat acid, both straight chain and branched chain, both mono-unsaturated and poly-unsaturated, are useful monomers for the preparation of the polymeric fat acids. Suitable examples of such materials include IO-undecynoic acid, tariric acid, stearolic acid, behenolic acid, and isamic acid.

Because of their ready availability and relative ease of polymerization, oleic and linoleic acid and mixtures thereof are the preferred starting materials for the preparation of the polymeric fat acids. The dimerized fat acid is then converted to the corresponding dinitrile by reacting the dimerized fat acid with ammonia under nitrile forming conditions. The details of this reaction are set forth in Chapter 2 of Fatty Acids and Their Derivatives by A. W. Ralston, John Wiley & Sons, Inc., New York (1948). If desired, the dinitrile may then be purified to the desired degree by vacuum distillation or other suitable means. Generally, the high purity dinitrile tends to produce linear polysecondary amines of high molecular weight. If appreciable amounts of mononitrile are present, the polymer will be of low molecular weight, since these materials act as chain stoppers. The presence of trinitriles and other higher polyfunctional nitriles tend to produce a cross-linked polymer. A sufiicient amount of trinitriles will provide a gelled product.

Copolymeric polysecondary amines can be prepared by copolymerizing mixtures of dinitriles. The desired dinitrile comonomer is added to the reaction mixture along with the fatty dinitrile. After subjecting the mixture to polymerization conditions, there is obtained a polysecondary amine copolymer having randomly distributed recurring units:

where D is a dimeric fat radical and R, is a divalent radical derived from the comonomer dinitrile. Generally, any copolymerizable dinitrile can be employed. Specific examples of simple nitriles which can be employed as comonomers include the dinitriles derived from such acids as adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. Mixtures of two or more fatty dinitriles can also be copolymerized. A large variety of other dinitriles are likewise useful.

In theory, the formation of the polymeric secondary amine proceeds through the preliminary reduction of the nitrile to the primary amine followed by conversion of the primary amine to the polymeric secondary amine. Accordingly, this provides an alternate route for the preparation of the polymers. In the alternate route, the polyamines are formed separately and then converted to the polymeric amines under the conditions previously described, although it is possible to use a variety of other polyamines as comonomers including some comonomers such as metaxylene diamines which may not be readily employed in the form of nitriles.

From a practical standpoint, there may be certain advantages in thus carrying out the preparation of the polymeric secondary amines in two steps since it makes possible the removal of any by-products formed in the first step, i.e., the formation of the primary amine and thus enhances the purity of the final product. In addition, the milder conditions used to form the polymeric secondary amine from the di-primary amine results in less degradation and thus further enhances the purity of the product.

Generally, the end groups of the polymers of the polymeric secondary amine will be either amine groups or nitrile groups. Where the polymers are prepared by condensing amines, all the end groups will be primary amines:

where D and n are as previously defined. Where a dinitrile is used as the starting material and the reaction'conditions are mild and the reaction times are short, the end groups will be mainly nitrile groups:

N CDCHZ[IIICH7DCH7],;NCH1DCN Into a 1 liter stirred autoclave were charged 417 grams of distilled dimer nitrile prepared from dimerized linoleic acid, and 10 grams of water-wet Raney nickel catalyst. The autoclave was flushed with hydrogen, sealed under p.s.ig. hydrogen and rapidly heated to 200 C., at which time a continuous venting of hydrogen was begun such that the hydrogen coming into the autoclave was at 240 p.s.i. and the actual pressure in the autoclave was approximately 230 p.s.i. Heating was continued until the desired reaction temperature of 270 C. was reached. The hydrogenation was continued at this temperature for a period of 1% hours. The reaction mixture was then cooled to below 200 C. and the catalyst was filtered 01f. There was obtained a product having a Bro-okfield viscosity of 114 poises at 25 C., a molecular weight of 4600 and an inherent viscosity of 0.165 as measured on a 0.5% solution in meta-cresol. Infrared analysis indicated that no nitrile groups were left in the product. The product contained 12.4% primary amine groups, 72.7% secondary amine groups, and 5.5% tertiary amine groups.

Example B Example A was repeated except 21 grams of a commercially available copper-chromite catalyst G-13, was substituted for the Raney nickel catalyst of Example A. There was obtained a product having a Brookfield viscosity of 4220 poises at 25 C., a molecular weight of 0.5%

solution in meta-cresol. The product contained 8.0% primary amine groups, 84.4% secondary amine groups, 5.1% tertiary amine groups, and no nitrile groups.

Example C Example B was repeated except that the reaction was run at 250 C., for a period of 5% hours. There was obtained a product having a Brookfield viscosity of 6200 poises at 25 C., a molecular weight of 11,000, and an inherent viscosity of 0.335 as measured on a 0.5% solution in meta-cresol. The product contained 6.5% primary amine groups, 85.9% secondary amine groups, 5.7% tertiary amine groups, and no nitrile groups.

Example D Example B was repeated except that the reaction time was increased to 2 hours. There was obtained a product having a Brookfield viscosity of greater than 20,000 poises at 25 C., a Brookfield viscosity of 6400 poises at 60 C., a molecular weight of 9900, and an inherent viscosity of 0.334 as measured on a 0.5% solution in meta-cresol. The product contained 7.0% primary amine groups, 8.14% secondary amine groups, 7.6% tertiary amine groups, and no nitrile groups.

Example E Into a 1 liter stirred autoclave were charged 400 grams of crude undistilled dimer nitrile prepared from vacuum stripped dimerized linoleic acid, and 100 grams monomer nitrile prepared from the recovered monomeric acid obtained from the polymerization of linoleic acid, and 25 grams of copper-chromite of Example B. After hydrogenation at 280 C. for 1% hours, there was obtained a product having a Brookfield viscosity of 241 poises at 25 C., 6.9% primary amine groups, 8.12% secondary amine groups, 5.6% tertiary amine groups, and 2.8% nitrile groups;

Example F A crude undistilled dimer nitrile prepared from vacuum stripped dimerized linoleic acid was treated with a mixture of copper-chromite catalyst recovered from the reaction mixture of a previous successful hydrogenation and diatomaceous earth. The level of catalyst used in this pretreatment was about 5% by weight, based on the nitrile. The dimer nitrile was recovered by filtration, Into a 1 liter stirred autoclave were charged 442 grams of the treated dimer nitrile and 21 grams of the copper-chromite catalyst of Example B. After hydrogenation at 280 C. for 1% hours, there was obtained a product having 9.2% primary amine groups, 71.9% secondary amine groups, 5.8% tertiary amine groups, and 5.6% nitrile groups. The product had a Brookfield viscosity of 639 poises at 25 C. and a molecular weight of 4200.

Example G A crude undistilled dimer nitrile prepared from vacuum stripped dimerized linoleic acid was treated with 1.5 grams of sodium hydroxide dissolved in ethanol. Thereafter 400 grams of the treated dimer nitrile .and 20 grams of the copper-chromite catalyst of Example B were charged into 1 liter autoclave. After hydrogenation at 280 C. for 1% hours there was obtained a product having a molecular weight of 3000, a Brookfield viscosity at 25 C. of greater than 20,000 poises and a Brookfield viscosity at 60 C. of 1,260 poises. Analysis of the product indicated that it had 15.8% primary amine groups, 60.7% secondary amine groups, 9.4% tertiary amine groups, and no nitrile groups.

Example H Into a 1 liter stirred autoclave were charged 530 grams of a distilled dimer nitrile having an iodine value of 8.5 prepared from a distilled dimer acid essentially saturated by hydrogenation having an iodine value of 8.4 and 25 grams of the copper-chromite catalyst of Example B.

After hydrogenation for 3 hours at 270 C., there was obtained a product having an apparent molecular weight of 5,800, an iodine value of 10.3, a Brookfield viscosity of 2,240 poises at 60 C. The product contained 9.6% primary amine groups, 76.7% secondary amine groups, 5.4% tertiary amine groups, and no nitrile groups.

Example I Example H was repeated except that 9.6 grams of methanol-wet Raney nickel was used as a catalyst for 400 grams of nitrile. After hydrogenation at 270 C. for 1% hours, there was obtained a gelled product.

Example 1 Into a 1 liter stirred autoclave were charged 405 grams of distilled dimer nitrile prepared from dimerized linoleic acid, 81 grams of adiponitrile, and 25 grams of the copper-chromite catalyst of Example B. After hydrogenation at 270 C. for 2 hours, there was obtained a copolymer product having 6.3% primary amine groups, 49.6% secondary amine groups, 18.1% tertiary amine groups, a Brookfield viscosity of 338 poises at 25 C., and a Brookfield viscosity of 60 poises at 60 C.

Example K Example A was repeated except that the hydrogenation was carried out at a reaction pressure of psi. for 4 hours at 232 to 248 C. using 10 g. of methanol-wet Raney nickel catalyst. There was obtained a product having 1% primary amine groups, 72.3% secondary amine groups, 6.1% tertiary amine groups, 11.8% nitrile groups, an iodine value of 83.4 and a Brookfield viscosity of 660 poises at 25 C.

Example L Into a 1 liter stirred autoclave was charged 300 grams of a distilled dimer diamine having a total amine number of 205.1 as compared to theoretical value of 204.2 which was prepared by hydrogenating dimer nitrile in the presence of ammonia, and 12 grams of methanol-wet Raney nickel catalyst. After hydrogenating the mixture for 2 hours using the conditions of Example A, there was obtained a polymeric product having 23.3% primary amine groups, 69.5% secondary amine groups, 4.8% tertiary amine groups, and a Brookfield viscosity of 65.2 poises at 25 C.

Example M Into a 1 liter stirred autoclave was charged 68 grams of meta xylylene diamine, 291 grams of the distilled dimer diamine of Example L, and 10 grams of the copper-chromite catalyst of Example B. After hydrogenating for 1 /3 hours using the reaction conditions of Example A, there was obtained a copolymeric product having an amine number due to secondary amines of 117.8. In comparison, the product of Example L had an amine number due to secondary amines of 76.6 and the product of Example C had an amine number .due to secondary amines of 90.3. The higher amine number for the product of this example indicates a larger weight percent of secondary amine groups due to formation of the copolymer.

The foregoing examples have been included as illustrations of the preparation of polysecondary amines and are not to be construed as limitations on the scope of the present invention.

The alkylation of a polysecondary amine to a polytertiary amine is conveniently carried out by treatment of the polysecondary amine with an organic halide and aqueous sodium hydroxide. The type of organic halide is not critical; all aliphatic and aromatic halides are generally useful. The sodium hydroxide absorbs and neutralizes the hydrochloric acid by-product of the reaction, thereby forcing the reaction to completion. Other bases, such as potassium hydroxide, barium hydroxide and sodium bicarbonate can be substituted for the sodium hydroxide if desired. Generally, it is preferred to carry out the alkylation at a temperature of about to 150 C.

The number of equivalents of the organic halide employed should be approximately equal to the number of amine groups of the polysecondary amines which are to be alkylated. Large excesses of the organic halide should be avoided otherwise side reactions will occur. Preparation of polymers containing both secondary and tertiary amine groups is accomplished by using smaller amounts of organic halide.

Examples of organic halides which can be employed include methyl chloride, ethyl chloride, butyl chloride, hexyl chloride, decyl chloride, stearyl chloride, l-hexenyl chloride, l-decenyl chloride, cyclohexylchloride, oleyl chloride, linoleyl chloride, benzyl chloride, chlorobenzene, 3-chloro-1,Z-dinitro-benzene, 1-chloro-4-fluorobenzene, methyl iodide, ethyl bromide, decyl bromide, chloronaphthalene, 1,4-dichlorobutene-2, dichlorobenzene, 1- chlorodecalin and, fl,fi'-dichloro-ethyl ether. Acetylenically unsaturated organic halides can be employed if desired, although they are generally not preferred because of high cost and comparative unavailability. The dihalides tend to produce cross-linked products.

The organic halides employed may be generally indicated by the formula R'X, where X is a halogen and, R is an aliphatic or aromatic hydrocarbon radical having from 1 to 20 carbon atoms. The preferred organic halides are the alkyl and alkenyl chlorides and bromides of 1 to 20 carbon atoms in which the alkyl or alkenyl radicals of 1 to .20 carbon atoms may be indicated as R".

If the desired amino substituents are methyl groups, the standard formaldehyde-formic acid methylation reaction can be employed. In this reaction formaldehyde is added to the amine group replacing the active amine hydrogens thereby forming a hydroxymethyl radical. The formic acid converts the hydroxymethyl groups to a methyl radi cal thereby forming the desired product. Higher carbon substituents can be introduced into the polysecondary amine by substituting a higher aldehyde for the formaldehyde.

If the end groups of the polysecondary amine are amine groups, they generally will be alkylated.

The invention will be better understood with reference to the following examples. Unless otherwise indicated, all parts and percentages are by weight.

Example I To a 1 liter stainless steel autoclave were charged 387 g. of a polymeric fatty secondary amine having a molecular weight of 3100 as determined by end groups analysis prepared according to the procedure of Example G, 50 g. distilled water, 50 g. isopropanol, 30.4 g. of paraformaldehyde and 42.0 g. of 90%, formic acid. The autoclave was sealed and heated to 115 C., the by-product water and carbon dioxide gases were vented intermittently to hold the pressure at 250 p.s.i.g. After one hour at 115 C., the autoclave was cooled to 50 C. and vented.

0 Approximately an equal volume of a solvent mixture containing 2 parts of butanol and 1 part of toluene was added along with 300 ml. of aqueous sodium hydroxide solution containing 0.825 equivalent of sodium hydroxide. A'fter shaking, the lower alkaline aqueous phase was withdrawn and the upper organic phase was washed with distilled water until'free of dissolved salts and sodium hydroxide. The organic layer was dried by filtering through anhydrous sodium sulfate and stripped free of solvent. There was obtained a pale, clear, light amber colored, viscous liquid having a total amine number of 98.9 and a tertiary amine number of 95.4. This indicates that 96.5% of the amine groups were tertiary.

Example II Example 111 Into a reaction kettle was loaded the following materials (in sequence listed):

lbs. polymeric secondary amine (molecular weight 9.25 lbs. paraformaldehyde (91%) 14.05 lbs. formic acid (88%) 12.5 lbs. distilled water 12.5 lbs. isopropanol The mixture was heated, with agitation, from 50 C. at a pressure of 10 p.s.i. to 115 C. at a pressure of 190 p.s.i. in 0.5 hour. These approximate conditions (115 C. and 190 p.s.i.) were maintained for 1.5 hours. The kettle and contents were then cooled. The resulting product was Washed and neutralized by employing 30 lbs. Skelly C (heptane), 70 lbs. isopropanol, lbs. hot distilled water, and 4 lbs. of ammonium hydroxide solution (30%). The pH of the water layer at this point was about 7. The wash procedure was repeated except an additional pound (1 lb.) of the sodium hydroxide solution was used. The pH of the water layer at this point was about 7. The wash procedure was repeated except an additional pound (1 lb.) of the sodium hydroxide solution was used. The pH of the water layer was about 8. The solvent was then stripped from the amine and the resulting product filtered through a 96 mesh silk screen. The product had the following properties:

Total amine 97.0 Tertiary amine 98.0 Gardner color' 10-11 Ju l CH2CH: 0

omoHlo omomon where m is as previously defined. In addition, epichlorohydrin or styrene oxide may also be used to provide additions such as on 111,3111 011201 or omg Acrylic adducts of the polysecondary amines may also be formed by reaction of the polysecondary amine with an acrylic compound of the formula R R I C=C.A

where R is a hydrogen, aryl or alkyl radical and A is selected from the group consisting of In general, R' is either hydrogen or a lower alkyl group having from 1 to 6 carbon atoms. cyanoethylation will provide polytertiary amino-propionitriles, which upon hydrogenation will yield polytertiary amino-propylamines. The amino-nitriles and propyl amines may be illustrated as follows:

where D is as previously defined. In the cyanoethylation reaction a slight equivalent excess of acylonitrile is used for each equivalent of secondary amine (each active hydrogen) in the presence of about methanol. The reaction is carried out at the acrylonitrile reflux temperature for about 3 hours, followed by stripping of the excess acrylonitrile and methanol at about 70 C. under vacuum to obtain the amino-nitrile. If desired, the nitrile is then hydrogenated at about 120 C. with 5-10% Raney nickel catalyst (washed with absolute methanol to remove water) at about 100-1000 p.s.i. of hydrogen containing several moles of ammonia.

The products of the present invention are highly effective corrosion inhibitors. They are also useful as asphalt anti-stripping agents, epoxy curing agents, fiocculents, liquid ion exchange agents, antistatic agents, fuel oil stabilizers, and carbohydrate modifying agents.

The embodiments of the present invention in which an exclusive property or privilege is claimed are defined as follows:

1. A polymer having the recurring structural unit where D is a hydrocarbon dimeric fat radical and R is selected from the group consisting of alkyl and alkenyl radicals having from 1 to 20 carbon atoms, benzyl, phenyl and naphthyl radicals.

2. A polymer as defined in claim 1 in which R is methyl and D is the hydrocarbon dimeric fat radical of dimerized linoleic acid.

3. A polymer of the structure where D is a hydrocarbon dimeric fat radical, x is an integer of from 2 to 40 and R is selected from the group consisting of alkyl and alkenyl radicals having from 1 to 20 carbon atoms, benzyl, phenyl and naphthyl radicals.

4. A polymer as defined in claim 3 in which R is methyl and D is the hydrocarbon dimeric fat radical of dimerized linoleic acid.

5. The polymer of the structure N ODOH [I-|I-CH1D- CH1-lx-I |ICHrD- CN wherein D is a hydrocarbon dimeric fat radical, x is an integer from 2 to 40 and R is selected from the group con sisting of alkyl and alkenyl radicals having from 1 to 20 carbon atoms, benzyl, phenyl and naphthyl radicals.

6. The polymer of claim 5 wherein D is the hydrocarbon dimeric fat radical of dimerized linoleic acid and R is methyl.

7. A polymer containing the recurring units [1TICH:D-CH1] and [-2 C r- 0- a-l where D is a hydrocarbon dimeric fat radical, R is se lected from the group consisting of the divalent m-xylylene radical and a divalent radical of a dinitrile of an acid selected from the group consisting of adipic, pimelic, suberic, azelaic and sebacic acids and R is selected from the group consisting of alkyl and alkenyl radicals having from 1 to 20 carbon atoms, benzyl, phenyl and naphthyl radicals.

References Cited by the Examiner UNITED STATES PATENTS 3,073,864 1/1963 Harrison et a] 260567.6

CHARLES B. PARKER, Primary Examiner.

ROBERT V. HINES, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent Not, 3,281,470 October 25, 1966 Leonard Ru Vertnik It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 1, line 38, for "coypolymerizable" read copolymerizable column 2, line 21, for "(132)" read (1932) column 3, line 3, for "acd" read acid column 8, lines 41 to 44, strike out "The pH of the water layer at this point was about 70 The wash procedure was repeated except an additional pound (1 1b,) of the sodium hydroxide solution was usedo"; same column 8, line 48, for "97.0" read 9758 column 10, line 9, for "H" read R Signed and sealed this 5th day of September 1967a (SEAL) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner of Patents 

1. A POLYMER HAVING THE RECURRING STRUCTURAL UNIT 